EP0415609B1 - Composition insecticide granulée - Google Patents

Composition insecticide granulée Download PDF

Info

Publication number
EP0415609B1
EP0415609B1 EP90309052A EP90309052A EP0415609B1 EP 0415609 B1 EP0415609 B1 EP 0415609B1 EP 90309052 A EP90309052 A EP 90309052A EP 90309052 A EP90309052 A EP 90309052A EP 0415609 B1 EP0415609 B1 EP 0415609B1
Authority
EP
European Patent Office
Prior art keywords
solvent
composition
orthene
pellets
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP90309052A
Other languages
German (de)
English (en)
Other versions
EP0415609A2 (fr
EP0415609A3 (en
Inventor
Jimmy Hua-Hin Chan
Rodrick I. Satre
James H. Trusler
Sadanand G. Memula
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron USA Inc
Original Assignee
Chevron USA Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chevron USA Inc filed Critical Chevron USA Inc
Publication of EP0415609A2 publication Critical patent/EP0415609A2/fr
Publication of EP0415609A3 publication Critical patent/EP0415609A3/en
Application granted granted Critical
Publication of EP0415609B1 publication Critical patent/EP0415609B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds
    • A01N57/28—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds containing acyclic or cycloaliphatic radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests

Definitions

  • This invention relates to pelletized insecticidal compositions and methods of making the same.
  • the present invention is concerned with making pelletized insecticidal N-hydrocarboyl phosphoroamidothioates and phosphoroamidodithioates.
  • N-hydrocarboyl phosphoroamidothioates and phosphoroamidodithioates have high insecticidal activity.
  • a particularly important commercial insecticide within these classes of compounds is the insecticide Orthene®, which can be systemically taken up by a plant so that insects which feed and/or live on the plant are killed, in addition to those insects which directly ingest or are contacted by the insecticide. See U.S. Patent Nos. 3,716,600, 3,845,172 and 3,914,417.
  • Orthene® is commercially produced as technical grade chemical of about 97 to 99.5% purity.
  • One method of formulating technical grade Orthene® for commercial use is to mix the technical grade powder with an anti-caking agent, such as fumed silica, and a wetting agent.
  • the wetting agent is utilized to wet the Orthene® and the anti-caking agent is used to prevent agglomeration of the Orthene® in its container.
  • the wetting agent is utilized to improve the spread-out of ORTHENE® when it is applied to crops as a spray solution, or when applied as a dust, after exposure to moisture via rain, dew, or irrigation.
  • the powdered commercial forms of ORTHENE® are available in dilutions referred to as ORTHENE® 90S, ORTHENE® 75S, ORTHENE® 50S, and in other commercial dilutions.
  • ORTHENE® has a characteristically objectionable odor (believed to be organothio compounds) which is compounded by the problems with dust.
  • ORTHENE® is available in liquid form, which minimizes or eliminates airborne contamination due to dust. However, due to storage stability limitations of solutions, its concentration is limited to a maximum of 25%, the balance being solvent and adjuvants. ORTHENE® in a liquid formulation has a solvent and packaging expense as well as a container disposal requirement that makes it less attractive to the consumer on the basis of price and empty container disposal requirements.
  • ORTHENE® An agglomerate form of ORTHENE® which also minimizes airborne contamination due to dust, has been constrained to dilute concentrations of ORTHENE® applied to large particles by spraying and then dried, or as a dilute concentration of ORTHENE® combined with binders and anti-caking agents to form agglomerates via processes known to those skilled in the art, such as, pan granulation, extrusion, fluid granulation, pelletizing.
  • concentration of ORTHENE® via these methods has heretofore been limited to a concentration no greater than about 36% to 50%, with known commercial products typically no more than 5% ORTHENE.
  • the limit on concentration of ORTHENE® was due to the melt property of ORTHENE® limiting the feasible operability of this form of product.
  • Concentration of active ingredient is further limited by the ability of binding agents to form agglomerates, i . e . a minimum amount of any particular binding agent is required in order to meet physical properties of attrition resistance, crush strength and bulk density.
  • concentration was due to the practical wetting ability of the receiving agglomerate. Too much liquid applied would form a mud.
  • commercial products require more handling and are less attractive formulations for applications of ORTHENE® made via solution spraying.
  • the ORTHENE® xx S formulations have problems due to the anti-caking agent ingredients. Anti-caking agents are not soluble in water (the typical application spray solvent) or other normal solvents.
  • ORTHENE® xx S Due to their insolubility, they can settle in the applicator's spray tank.
  • the settled anti-caking agents plug spray nozzles which detracts from the marketability of the ORTHENE® xx S product line.
  • This spray nozzle plugging problem can occur when ORTHENE® xx S products are tank mixed with other commercial pesticides, which is a normal farming industry practice. While methods to minimize the occurrence of anti-caking agent settling have evolved, they require special procedures to avoid nozzle plugging conditions, which adds to the inconvenience of using ORTHENE® xx S.
  • anti-caking agent segregates in the manufacturing process equipment during material handling procedures and forms insoluble bits of anti-caking agent which can cause nozzle plugging.
  • ORTHENE® powders that resolve problems characteristic of dusts are desired by both the manufacturer and the marketplace.
  • One possible alternative to a powdered ORTHENE® is in the form of a pellet: a cylindrically shaped solid. Pellets practically eliminate the dust problems and reduce the surface area-to-weight ratio which mitigates the odor problem.
  • ORTHENE® pellets contain relatively small amounts of ORTHENE®, typically no more than 5% active ingredient. Attempts to manufacture technical assay (approximately 97% active ingredient) ORTHENE® pellets from the dry ORTHENE® technical powder have been unsuccessful. The anti-caking agents and binders needed to make the currently available ORTHENE® pellets add to product cost, can cause excess wear and tear on equipment, and by dint of being a major fraction of the product formula, require more bulk product than the concentrated powders in order to deliver effective amounts of ORTHENE® to the protected crop.
  • ORTHENE® pellets have the same water insolubility problem that the anti-caking agent has in ORTHENE® powdered formulae. Because of that, commercial ORTHENE® pellet products are limited to use by direct application to the crop; i . e ., placing individual pellets on or around each plant, which is impractical for most commercial farming ventures.
  • the present invention provides insecticidal compositions comprising pellets which contain as active insecticidal ingredients, at least 75% by weight of a compound or mixture of compounds of the formula: wherein R and R 1 individually are alkyl, alkenyl or alkynyl of up to 6 carbon atoms, R 3 is hydrogen or alkyl of 1-6 carbon atoms, R 2 is hydrogen, alkyl of 1-18 carbon atoms, cycloalkyl of 3-8 carbon atoms, alkenyl of 2-18 carbon atoms or alkynyl of 3-18 carbon atoms, and Y is oxygen or sulfur; and the pellets are characterized by an attrition resistance of at least about 92%, a mean hardness of greater than about 6.67 N (1.5 lb-F) and a bulk density of at least about 42 lb/ft 3 (about 0.68 gm/cc).
  • Methods are also provided for making such solid pellets by extrusion or molding of a pourable or moldable composition of the insecticide with a solvent, or of a hot melt of the insecticide.
  • concentration of ORTHENE® in these pellets is in the range of about 75% to 97% a.i., with the most likely concentration of 97% a.i.
  • the pellets according to the present invention are characterized by an attrition resistance of at least about 92%, a mean hardness of greater than about 6.67 N (1.5 lb-F) and a bulk density of at least about 42 lb/ft 3 (0.68 gm/cc) and may be made to any convenient size.
  • Useful pellets will be extrudates of about 3 mm to 25 mm in length with diameters from about 1.5 mm to 7 mm.
  • Spherical pellets are also useful having diameters of about 1 mm to 5 mm.
  • the active insecticidal ingredient of the pellets will be a compound or a mixture of compounds of the formula: wherein R, R 1 , R 2 , R 3 and Y are as described hereinabove.
  • Particularly preferred compounds are those in which R and R 1 are independently methyl, ethyl, allyl or alkenyl; R 2 is H or alkyl; and R 3 is hydrogen; and Y is oxygen.
  • the most preferred compound is that in which R, R 1 , and R 2 are methyl, R 3 is hydrogen and Y is oxygen.
  • This is the compound whose common name is acephate and is sold under the Trade Mark "Orthene”.
  • Compounds of the above formula may be prepared as described in technical form in Patent Nos.3,716,600, 3,845,600 and 3,914,417 which usually provide compositions of about 97-98.5% purity.
  • This technical grade insecticide may optionally be admixed with one or more additives prior to being pelletized as described hereinafter.
  • One additive may be ammonium sulfate, generally in an amount less than about 5% by weight of the total pellet composition, preferably 2% or less by weight of the total pellet composition. This small amount of ammonium, sulfate imports a slight acidity to the pellet composition which is desirable for stability.
  • Another additive may be anhydrous magnesium sulfate, generally in amount up to about 5% by weight of the total pellet composition, preferably 2% or less by weight. This serves as a dehydrating agent will absorb trace amounts of water present in the pellets to prevent hydrolysis of the insecticide.
  • surfactants may also be utilized, usually less than 20% by weight of the total composition, which would assist in dispersion of the insecticide on the crops.
  • Potential surfactants include various polymeric surfactants which are known by the trade name "Pluronic®” series and “Tetronic®” series sold by BASF.
  • Another additive may comprise a small amount of an anti-caking agent, generally less than about 1% by weight, and usually at least about 0.1% by weight of the total dry pellet composition. While an anti-caking agent is not necessary, it is preferred, particularly for prolonged storage of the pellets since the pellets may lightly cohere when exposed to high humidity, temperature or pressure.
  • the anti-caking agent can be applied to the pellets as a coating.
  • the preferred anti-caking agent is a fumed silica sold under the trade name Wessalon S.
  • the pellets are made by making a pourable or extrudable mixture of the solid technical insecticide composition with a solvent, optionally containing the dry additives.
  • the solvent should be selected such that the insecticidal composition has a solubility in that solvent at 20°C of at least about 0.5 gm/100 ml.
  • the solvent should also have a relatively high volatility at atmospheric pressure so that the pellets may be dried ( i . e ., freed of solvent) without or with only minimal application of heat.
  • exemplary solvents are hexane, carbon tetrachloride, toluene, isopropanol, ethanol, chloroform, methanol, methylene chloride and water.
  • the most preferred solvent is methylene chloride. Table 1 shows properties typical to pellets made using different solvents.
  • the dry ingredients (comprising the insecticide and additives, if present) are mixed with the solvent, preferably methylene chloride, in amount of about 3-25% by weight of solvent.
  • the proper amount of solvent will form an extrudable mixture having the consistency of damp sandy loam (as is used in the field of materials science) and form dry pellets having the properties given above within the scope of the invention.
  • the amount of solvent required to form the proper consistency and to yield the desired pellet properties is inversely relative to the solubility of the insecticide in the solvent, i . e ., the more soluble the insecticide the less solvent is needed to attain the desired consistency.
  • a damp sandy loam extrudable mix is the visual physical appearance of the pre-pelleted feed, the chemical characteristic of the feed is a function of the solvent and solute relationship, thus each "mix" has unique performance characteristics.
  • liquids are added to the mix in the form of lubricating agents or binders
  • liquids i . e . solvents
  • solvents are added to modify the ORTHENE® technical in order to form an improved "plastic" range of the extrusion mixture.
  • the mixture is extruded through an extruder having appropriately-sized orifices, conveniently under an L/d extrusion performance ratio of about 8.
  • the L/d performance ratio is a well known term in the extrusion art and relates the effective thickness of a die to the diameter of a pellet attained.
  • the heat caused from the pressure of extrusion will contemporaneously evaporate a substantial portion of the solvent from the extrusion product as it is formed, which is an advantage of the present invention. Any residual solvent can be removed by vacuum and/or air drying the extruded product, or by application of direct or indirect heat, if necessary. As the extrusion product exits the extruding orifice, the product is cut to appropriate size, usually about 3 mm to 10 mm in length.
  • the dry ingredients including the insecticidal compound may be mixed with a suitable solvent to form a flowable mixture, which may be, but need not necessarily be, a solution.
  • a suitable solvent to form a flowable mixture
  • the flowable mixture is then placed into a mold or other container and the solvent is evaporated to form a solid molded form.
  • the solid molded form is then released from the mold. Since the flowable mixture is not extruded, the amount of solvent is not particularly critical and the dry ingredients-to-solvent ratio to form the flowable mixture may be, for example, in the range of about 5-80% by weight of solvent.
  • the mold may be in the form of, for example, bricks or stakes to form a solid insecticidal composition.
  • the molds may also be in the form of pills, pellets or tablets so that when released from the mold the composition is already in a pelletized form.
  • the composition may be molded as a solid form, such as a brick, and then divided into fragments, such as by cutting or impact fragmentation and sieved to the desired size.
  • insecticidal compound (with or without the additives) in technical form may be melted (Orthene® melts at about 90°C) and the melt may be placed in a mold to form bricks, tablets, pellets, and the like.
  • the bricks may be again divided into fragments by cutting or fragmentation, etc.
  • the melt of insecticidal compound may be passed through an orifice to form pellet-sized drops and then the drops will be solidified.
  • the drops are solidified by dropping onto a cold surface, i . e , a surface which is at a temperature lower than the temperature of the drops.
  • a polymeric surfactant may be added in the amount of about 20% or less, by weight, to assist in the dispersion of the formulation on crops.
  • pellets according to the present invention will have an attrition resistance of at least 92% as determined by ASTM method D4058-87 on 5 mm (length) x 2.38 mm (diam.) pellet.
  • the mean hardness will also be greater than about 6.67 N (1.5 lb-F) as determined by ASTM method D3313-88, and bulk density will be at least about 42 lb/ft 3 (about 0.68 gm/cc).
  • pellets of ORTHENE® made in accordance with the present invention will exhibit improved odor control over commercial powdered formulations, such as ORTHENE® 75S.
  • Organothio odor is generally reduced by a factor at least 10 (ambient storage conditions) and thermal stability is improved over that of ORTHENE® 75S.
  • ORTHENE® tech 2% Ammonium sulfate 4.76 mm 1.5 kg 20.42(4.59) 0.92 3′32 ⁇ 4.
  • ORTHENE® tech Mfg. (2 min. spin) 4.76 mm 1.5 kg 36.72(6.06) 2.38 4′41 ⁇ 5.
  • ORTHENE® tech Ammonium sulfate 2% Alpine 0.5% 4.76 mm 1.5 kg 16.64(3.74) 0.71 -- 8.
  • ORTHENE® tech 99% 2.38 mm 1.5 kg 9.07(2.04) 0.43 2′06 ⁇ 9.
  • ORTHENE® tech Alpine 0.5% 2.38 mm 1.5 kg 10.54(2.37) 0.54 -- 10.
  • ORTHENE® tech Magnesium sulfate 1.59 mm 3.0 kg -- -- -- 14.
  • ORTHENE® tech Ammonium sulfate 1.59 mm 3.0 kg -- -- -- -- 14.
  • Pellets were made from tech Orthene® using different solvents. Different samples were used using 3-25% of each of the following solvents: chloroform, carbon tetrachloride, dichloroethane, deionized water, toluene, methanol, ethanol and isopropanol. Except in the case of toluene, carbon tetrachloride, isopropanol and dichloroethane, pellets were formed with sufficient physical properties to meet the parameters of the present invention. When using the alcohols and water, the initial extruded product was slightly wetter than when using the chlorinated solvents, however, the pellets could be dried to remove the moisture. Solubilities are given below for common solvents.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Claims (20)

  1. Composition insecticide sous forme de granules contenant, comme insecticide actif, au moins 75 % en poids d'un composé de formule générale :
    Figure imgb0008
     où R et R1 représentent individuellement un groupe alkyle, alcényle ou alcynyle ayant jusqu'à 6 atomes de carbone ; R3 est l'hydrogène ou un groupe alkyle ayant de 1 à 6 atomes de carbone ; R2 est l'hydrogène, un groupe alkyle ayant de 1 à 18 atomes de carbone, un groupe cycloalkyle ayant de 3 à 8 atomes de carbone, un groupe alcényle ayant de 2 à 18 atomes de carbone ou un groupe alcynyle ayant de 3 à 18 atomes de carbone, et Y est l'oxygène ou le soufre, les granules étant caractérisés en ce qu'ils ont une résistance à l'attrition d'au moins 92 %, une dureté moyenne supérieure à 6,67 N (1,5 lb-F) et une densité apparente d'au moins 42 livres/pied cubique (0,68 g/cm3).
  2. Composition selon la revendication 1 et comprenant, en outre, un agent tensio-actif.
  3. Composition selon la revendication 1 ou 2 et comprenant, en outre, du sulfate d'ammonium.
  4. Composition selon la revendication 3, dans laquelle le sulfate d'ammonium est présent en une quantité inférieure à 5 % en poids de la composition.
  5. Composition selon la revendication 1, 2, 3 ou 4, et comprenant, en outre, du sulfate de magnésium anhydre.
  6. Composition selon la revendication 5, dans laquelle le sulfate de magnésium anhydre représente jusqu'à 5 % en poids de la composition.
  7. Composition selon l'une quelconque des revendications précédentes, et comprenant, en outre, un agent empêchant l'agglutination.
  8. Composition selon la revendication 7, dans laquelle l'agent empêchant l'agglutination représente moins de 1 % en poids de la composition.
  9. Composition selon l'une quelconque des revendications précédentes, dans laquelle R et R1 sont indépendamment le groupe méthyle, éthyle, allyle ou alcényle ; R2 est H ou un groupe alkyle ; R3 est l'hydrogène, et Y est l'oxygène.
  10. Composition selon la revendication 9, dans laquelle R, R1 et R2 signifient le groupe méthyle, et R3 est l'hydrogène.
  11. Procédé de préparation d'une composition insecticide selon la revendication 1, comprenant les étapes consistant à :
    (a) former un mélange extrudable comprenant ledit composé dans 3 à 25 % en poids d'un solvant dans lequel ledit composé a une solubilité d'au moins 0,5 g/100 ml (à 20°C) et
    (b) former des granules à partir dudit mélange extrudable, par extrusion de celui-ci.
  12. Procédé selon la revendication 11 et comprenant, en outre, l'étape (c) consistant à appliquer un agent empêchant l'agglutination en tant que revêtement sur lesdits granules.
  13. Procédé selon la revendication 11 ou 12, dans lequel ledit solvant est le chlorure de méthylène.
  14. Procédé de préparation d'une composition insecticide selon la revendication 1, comprenant les étapes consistant à :
    (a) former un mélange ou une solution apte à s'écouler, comprenant ledit composé et un solvant dans lequel ledit composé est soluble à raison d'au moins 0,5 g/100 ml (à 20°C) ;
    (b) placer ledit mélange dans un moule ;
    (c) évaporer ledit solvant pour former une forme moulée solide ;
    (d) retirer ladite forme moulée dudit moule ; et
    (e), si cela est nécessaire, diviser ladite forme moulée en une pluralité de fragments.
  15. Procédé selon la revendication 14, dans lequel ledit solvant est le chlorure de méthylène.
  16. Procédé de préparation d'une composition insecticide selon la revendication 1, comprenant les étapes consistant à :
    (a) placer ledit composé à l'état fondu dans un moule ;
    (b) solidifier ladite forme fondue pour produire une forme moulée solide ;
    (c) retirer ladite forme moulée solide dudit moule ; et
    (d) si cela est nécessaire, diviser ladite forme moulée en une pluralité de fragments.
  17. Procédé de préparation d'une composition insecticide selon la revendication 1, comprenant les étapes consistant à :
    (a) faire passer ledit composé à l'état fondu à travers un orifice pour former des gouttes fondues dudit composé, de la dimension d'un granule ; et
    (b) solidifier lesdites gouttes.
  18. Procédé selon la revendication 17, dans lequel l'étape (b) comprend la mise en contact desdites gouttes avec une surface, ladite surface étant à une température inférieure à la température desdites gouttes.
  19. Utilisation d'un solvant organique pour la production d'une composition insecticide sous forme de granules selon la revendication 1, contenant un insecticide à base de phosphoroamidothioate ou de phosphoroamidodithioate de N-hydrocarboyle ayant la formule générale définie dans la revendication 1, dans le but de modifier l'insecticide pour augmenter son aptitude à être transformé en granules, ledit solvant étant un solvant dans lequel l'insecticide a une solubilité d'au moins 0,5 g/100 ml à 20°C.
  20. Utilisation d'un phosphoroamidothioate ou d'un phosphoroamidodithioate de N-hydrocarboyle fondu répondant à la formule générale définie dans la revendication 1 pour la production d'une composition insecticide sous forme de granules selon la revendication 1, les granules ayant une résistance à l'attrition d'au moins 92 %, une dureté moyenne supérieure à 6,67 N (1,5 lb-F) et une densité apparente d'au moins 42 livres/pied cubique (0,68 g/cm3).
EP90309052A 1989-08-18 1990-08-17 Composition insecticide granulée Expired - Lifetime EP0415609B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US395969 1989-08-18
US07/395,969 US5464623A (en) 1989-08-18 1989-08-18 Process for pelletizing insecticidal N-hydrocarboyl phosphoroamidothioates and phosphoroamidodithioates

Publications (3)

Publication Number Publication Date
EP0415609A2 EP0415609A2 (fr) 1991-03-06
EP0415609A3 EP0415609A3 (en) 1992-09-23
EP0415609B1 true EP0415609B1 (fr) 1997-11-19

Family

ID=23565317

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90309052A Expired - Lifetime EP0415609B1 (fr) 1989-08-18 1990-08-17 Composition insecticide granulée

Country Status (12)

Country Link
US (1) US5464623A (fr)
EP (1) EP0415609B1 (fr)
KR (1) KR0180214B1 (fr)
AT (1) ATE160256T1 (fr)
AU (1) AU647036B2 (fr)
BR (1) BR9004083A (fr)
CA (1) CA2023294C (fr)
DD (1) DD300502A5 (fr)
DE (1) DE69031724T2 (fr)
IL (1) IL95344A (fr)
NZ (1) NZ234835A (fr)
TW (1) TW214507B (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5352674A (en) * 1991-03-25 1994-10-04 Valent U.S.A. Chemically stable granules containing insecticidal phosphoroamidothioates
AU658186B2 (en) * 1991-03-25 1995-04-06 Amvac Chemical Corporation Chemically stable granules containing insecticidal phosphoroamidothioates
US5648486A (en) * 1992-07-13 1997-07-15 Cytomed, Inc. Compounds and methods for the treatment of inflammatory and immune disorders
FR2706247B1 (fr) * 1993-06-16 1996-10-11 Sumitomo Chemical Co Procédé de stabilisation de compositions pesticides contenant de l'acéphate, et compositions pesticides obtenues.
US6013272A (en) * 1996-12-19 2000-01-11 Valent U.S.A. Corporation Chemically stable, insecticidally active phosphoroamidothioate pellet compositions and methods for their manufacture
US6177412B1 (en) 1999-05-28 2001-01-23 Valent U.S.A. Corporation Insecticidal composition and method for the use thereof
US7157094B2 (en) * 2001-03-09 2007-01-02 Arysta Lifescience North America Group Granulated active ingredients
US6875381B2 (en) 2001-12-18 2005-04-05 United Phosphorus, Ltd. Process for preparation of chemically stable, dry-flow, low compact, dust free, soluble granules of phosphoroamidothioates
US20050147666A1 (en) * 2002-03-06 2005-07-07 Kyowa Hakko Kogyo Co., Ltd. Tablets quickly disintegrating in oral cavity
US6752943B1 (en) 2002-12-31 2004-06-22 United Phosphorus, Ltd. Apparatus and process for granulating dry powder materials
US7074355B2 (en) * 2003-09-02 2006-07-11 United Phosphorus Ltd. Process for dry granulation by agitative balling for the preparation of chemically stable, dry-flow, low compact, dust free, soluble spherical granules of phosphoroamidothioate
US8221776B1 (en) 2006-05-19 2012-07-17 Sander William A Phosphoroamidothioate granules and methods of manufacture thereof
US20080064663A1 (en) * 2006-09-11 2008-03-13 Gaytan Jesse H Melt processing of phosphoroamido(di)thioate insecticides
US20220104498A1 (en) * 2019-02-07 2022-04-07 Upl Ltd Insecticidal compositions resistant to active ingredient degradation and process for preparation thereof

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR985549A (fr) * 1949-02-23 1951-07-19 Nouveau mode de présentation et d'utilisation de produits insecticides ou autres
US3716600A (en) * 1970-02-24 1973-02-13 Chevron Res N-acyl derivatives of phosphoroamidothioates
US3845172A (en) * 1971-05-28 1974-10-29 Chevron Res N-hydrocarboyl phosphoroamido-thioates and phosphoroamidodithioates
US3914417A (en) * 1972-12-21 1975-10-21 Chevron Res Insectidical N-hydrocarboyl phosphoroamidothioates and phosphoroamidodithioates
US4183740A (en) * 1978-01-05 1980-01-15 American Cyanamid Company Solid compositions of a liquid surfactant and a pyrazolium herbicide
JPS58188801A (ja) * 1982-04-27 1983-11-04 Yashima Sangyo Kk 害虫駆除用農薬杭
JPS61136721A (ja) * 1984-12-05 1986-06-24 Fuji Bureede Kk ソ−チエン用カツテイングリンク
US4683224A (en) * 1985-09-18 1987-07-28 E. I. Du Pont De Nemours And Company N-formyl phosphonamidothioates as pesticides
JP2518631B2 (ja) * 1987-01-22 1996-07-24 クミアイ化学工業株式会社 固状・農薬組成物
EP0321527B1 (fr) * 1987-07-01 1992-08-12 Ici Australia Operations Proprietary Limited Granules se dispersant dans l'eau
GB8827031D0 (en) * 1988-11-18 1988-12-21 Ici Plc Insecticidal compositions

Also Published As

Publication number Publication date
EP0415609A2 (fr) 1991-03-06
CA2023294A1 (fr) 1991-02-19
CA2023294C (fr) 1998-05-12
DE69031724D1 (de) 1998-01-02
TW214507B (fr) 1993-10-11
DD300502A5 (de) 1992-06-17
KR910004096A (ko) 1991-03-28
AU6111290A (en) 1991-02-21
US5464623A (en) 1995-11-07
ATE160256T1 (de) 1997-12-15
KR0180214B1 (ko) 1999-04-01
BR9004083A (pt) 1991-09-03
DE69031724T2 (de) 1998-06-04
NZ234835A (en) 1992-08-26
IL95344A (en) 1997-02-18
EP0415609A3 (en) 1992-09-23
IL95344A0 (en) 1991-06-30
AU647036B2 (en) 1994-03-17

Similar Documents

Publication Publication Date Title
CA2047755C (fr) Bouletage de derives de phosphoroamidothioate avec des engrais et des pesticides
EP0415609B1 (fr) Composition insecticide granulée
US5100667A (en) Process for pelletizing insecticidal N-hydrocarboyl phosphoroamidothioates and phosphoroamidodithioates
US7157094B2 (en) Granulated active ingredients
JPS59193803A (ja) 物理性の改良された顆粒状水和剤
KR20070060046A (ko) 화학적 안정적, 건조 유동식, 저밀도, 먼지 없는, 구형의가용성 포스포로아미도티오에이트 과립 제조용 교반식볼링에 의한 건조 과립 제조 방법
JP5145539B2 (ja) 水溶性農薬殺虫成分を溶出コントロールした育苗箱水稲用粒剤
US6875381B2 (en) Process for preparation of chemically stable, dry-flow, low compact, dust free, soluble granules of phosphoroamidothioates
AU607167B2 (en) Safened pesticidal dispersion resin compositions for controlling soil borne pests and process for the preparation thereof
JP2007284429A (ja) コーティング型育苗箱水稲用粒剤およびその製造方法
HU203937B (en) Sorptive granulated compositions against soil pesticides, comprising thiophosphoric acid derivative
JPH0542403B2 (fr)
WO1997009882A1 (fr) Sable enduit de phosphoroamidothioate et procede correspondant
JPH0517302A (ja) 粒状物質およびその製造方法
JP2879802B2 (ja) 農薬粒剤の製造方法
KR20090060338A (ko) 포스포로아미도（디）티오에이트 살충제의 용융 가공방법
TW202146362A (zh) 穩定化的含尿素肥料摻合物
JP2003055106A (ja) 粒状殺虫組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19921102

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CHEVRON U.S.A. INC.

17Q First examination report despatched

Effective date: 19950317

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19971119

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19971119

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19971119

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19971119

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19971119

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19971119

REF Corresponds to:

Ref document number: 160256

Country of ref document: AT

Date of ref document: 19971215

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69031724

Country of ref document: DE

Date of ref document: 19980102

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980219

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: E. BLUM & CO. PATENTANWAELTE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980817

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: CHEVRON U.S.A. INC.

Free format text: CHEVRON U.S.A. INC.#1635 MARKET STREET#PHILADELPHIA PENNSYLVANIA 19103 (US) -TRANSFER TO- CHEVRON U.S.A. INC.#1635 MARKET STREET#PHILADELPHIA PENNSYLVANIA 19103 (US)

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20090806

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20090708

Year of fee payment: 20

Ref country code: NL

Payment date: 20090814

Year of fee payment: 20

Ref country code: CH

Payment date: 20090811

Year of fee payment: 20

Ref country code: DE

Payment date: 20090831

Year of fee payment: 20

REG Reference to a national code

Ref country code: NL

Ref legal event code: V4

Effective date: 20100817

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20100816

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20100817

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20100816

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20100817